Morphological development and rheological changes of phenoxy/SAN blends during in‐situ polymerization

This article reports the results of an investigation into the time‐dependent morphological and rheological changes that accompany the in‐situ polymerization of blends composed of poly(hydroxyether of bisphenol A) (phenoxy) and poly(styrene‐co‐acrylonitrile) (SAN). The rheological behavior was monitored continuously during the in‐situ polymerization, whereas the miscibility and phase structure of blends formed in situ were examined at discrete stages of polymerization by differential scanning calorimetry and transmission electron microscopy. In the blend with 30 wt % SAN, a co‐continuous blend morphology was associated with gradual changes in the dynamic moduli, suggesting that phase separation proceeded by spinodal decomposition (SD). In contrast, phenoxy‐rich dispersions were uniformly dispersed in a continuous SAN‐rich matrix in the blend with 50 wt % SAN, and the corresponding rheological signature revealed a sharp initial increase in the dynamic moduli, followed by slower growth after long times, indicative of phase separation via nucleation and growth (NG). The rheological property changes are closely related to morphology development and mechanisms of phase separation induced duringin‐situ polymerization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2614–2619, 2007     

Poly(hydroxyether of bisphenol A)/poly(vinyl acetate) blends: In situ polymerization preparation,morphology, and properties

The blends of poly(hydroxyether of bisphenol A) (phenoxy) and poly(vinyl acetate) (PVAc) were prepared through in situ polymerization, i.e., the melt polymerization of diglycidy ether of bisphenol A (DGEBA) and bisphenol A in the presence of PVAc. The polymerization reaction started from the initial homogeneous ternary mixture of PVAc/DGEBA/bisphenol A; the phase separation induced by reaction occurred as the polymerization proceeded. The phenoxy/PVAc blends with PVAc content up to 20 wt % were obtained and were further characterized by the solubility, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and scanning electronic microscopy (SEM). The results indicate that no intercomponent reaction occurred during the in situ polymerization. All the blends display separate glass transition temperatures (Tg's); the very fine phase-separated morphology was obtained by this polymerization blending method. Mechanical tests show that the prepared blends exhibited substantial improvement of mechanical properties, especially in impact strength, which could be ascribed to the formation of the fine phase-separation morphology during in situ polymerization. The thermogravity analysis (TGA) of the blends showed that the thermal stability of the PVAc-rich phases in the blends was enhanced in comparison to the pure PVAc due to the synergistic contribution of the two phases in energy transportation. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2329–2338, 1999     

Upper critical solution temperature type phase behavior of poly(styrene‐co‐acrylonitrile) blends with poly(styrene‐co‐n‐phenyl maleimide) and their interaction energies

To enhance the heat resistance of poly(styrene‐co‐acrylonitrile‐co‐butadiene), ABS, miscibility of poly(styrene‐co‐acrylonitrile), SAN, with poly(styrene‐co‐n‐phenyl maleimide), SNPMI, having a higher glass transition temperature than SAN was explored. SAN/SNPMI blends casted from solvent were immiscible regardless of copolymer compositions. However, SNPMI copolymer forms homogeneous mixtures with SAN copolymer within specific ranges of copolymer composition upon heating caused by upper critical solution temperature, UCST, type phase behavior. Since immiscibility of solvent casting samples can be driven by solvent effects even though SAN/SNPMI blends are miscible, UCST‐type phase behavior was confirmed by exploring phase reversibility. When copolymer composition of SNPMI was fixed, the phase homogenization temperature of SAN/SNPMI blends was increased as AN content in SAN copolymer increased. To understand the observed phase behavior of SAN/SNPMI blend, interaction energies of blends were calculated from the UCST‐type phase boundaries by using the lattice‐fluid theory combined with a binary interaction model. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1131–1139, 2008     

Evaluation of the interaction parameter for poly(ε‐caprolactone)/poly(styrene‐co‐acrylonitrile) blends

In this article, the miscibility of poly(ε‐caprolactone) (PCL) with poly(styrene‐co‐acrylonitrile) (SAN) containing 25 wt % of acrylonitrile is studied from both a qualitative and a quantitative point of view. The evidences coming from thermal analysis (differential scanning calorimetry) demonstrate that PCL and SAN are miscible in the whole range of composition. The Flory interaction parameter χ_1,2 was calculated by the Patterson approximation and the melting point depression of the crystalline phase in the blends; in both cases, negative values of χ_1,2 were found, confirming that the system is miscible. The interaction parameter evaluated within the framework of the mean field theory demonstrates that the miscibility of PCL/SAN blends is due to the repulsive interaction between the styrene and acrylonitrile segments in SAN. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Analysis of blends of poly(styrene‐co‐acrylonitrile) with an epoxy/aromatic amine resin using scanning thermal microscopy

Using a microthermal analyzer TA Instruments 2990 μTA, we have analyzed the morphologies developed for the resin tetraglycidyl‐4,4′‐diaminodiphenylmethane cured with an aromatic amine 4,4′‐diaminodiphenylsulphone modified with different amounts of poly(styrene‐co‐acrylonitrile) (SAN) thermoplastic. The phase‐separation phenomenon induced by polymerization was also followed by scanning electron microscopy. Using the modulated local thermal‐analysis mode of μTA, the glass‐transition temperatures of different domains for each sample were evaluated. Dynamic mechanical analyzer experiments were made to evaluate the macroscopic thermal properties of the blends. A morphology was well established for all blends examined with these techniques showing a nodular structure, the epoxy‐rich phase, and a continuous phase, the SAN‐rich phase, that forms the matrix. From both microscopic and macroscopic thermal analyses, it is concluded that a phase separation exists for the blends investigated. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 284–289, 2002     

Competitive hydrogen bonding and self‐assembly in poly(2‐vinyl pyridine)‐block‐poly(methyl methacrylate)/poly(hydroxyether of bisphenol A) blends

Blends of poly(2‐vinyl pyridine)‐block‐poly(methyl methacrylate) (P2VP‐b‐PMMA) and poly(hydroxyether of bisphenol A) (phenoxy) were prepared by solvent casting from chloroform solution. The specific interactions, phase behavior and nanostructure morphologies of these blends were investigated by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), dynamic light scattering (DLS), atomic force microscopy (AFM), and transmission electron microscopy (TEM). In this block copolymer/homopolymer blend system, it is established that competitive hydrogen bonding exists as both blocks of the P2VP‐b‐PMMA are capable of forming intermolecular hydrogen bonds with phenoxy. It was observed that the interaction between phenoxy and P2VP is stronger than that between phenoxy and PMMA. This imbalance in the intermolecular interactions and the repulsions between the two blocks of the diblock copolymer lead to a variety of phase morphologies. At low phenoxy concentration, spherical micelles are observed. As the concentration increases, PMMA begins to interact with phenoxy, leading to the changes of morphology from spherical to wormlike micelles and finally forms a homogenous system. A model is proposed to describe the self‐assembled nanostructures of the P2VP‐b‐PMMA/phenoxy blends, and the competitive hydrogen bonding is responsible for the morphological changes. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1894–1905, 2009     

Phase behavior of tetramethylpolycarbonate blends with styrene‐based methacrylate copolymers and their interaction energies

The miscibility of tetramethylpolycarbonate (TMPC) blends with styrenic copolymers containing various methacrylates was examined, and the interaction energies between TMPC and methacrylate were evaluated from the phase‐separation temperatures of TMPC/copolymer blends with lattice‐fluid theory combined with a binary interaction model. TMPC formed miscible blends with styrenic copolymers containing less than a certain amount of methacrylate, and these miscible blends always exhibited lower critical solution temperature (LCST)‐type phase behavior. The phase‐separation temperatures of TMPC blends with copolymers such as poly(styrene‐co‐methyl methacrylate), poly(styrene‐co‐ethyl methacrylate), poly(styrene‐co‐n‐propyl methacrylate), and poly(styrene‐co‐phenyl methacrylate) increase with methacrylate content, go through a maximum, and decrease, whereas those of TMPC blends with poly(styrene‐co‐n‐butyl methacrylate) and poly(styrene‐co‐cyclohexyl methacrylate) always decrease. The calculated interaction energy for a copolymer–TMPC pair is negative and increases with the methacrylate content in the copolymer. This would seem to contradict the prediction of the binary interaction model, that systems with more favorable energetic interactions have higher LCSTs. A detailed inspection of lattice‐fluid theory was performed to explain such phase behavior. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1288–1297, 2002     

Effect of PBT molecular weight and reactive compatibilization on the dispersed‐phase coalescence of PBT/SAN blends

Poly(butylene terephthalate) (PBT)/styrene‐acrylonitrile copolymer (SAN) blends were investigated with respect to their phase morphology. The SAN component was kept as dispersed phase and PBT as matrix phase and the PBT/SAN viscosity ratio was changed by using different PBT molecular weights. PBT/SAN blends were also compatibilized by adding methyl methacrylate‐co‐glycidyl methacrylate‐co‐ethyl acrylate terpolymer, MGE, which is an in situ reactive compatibilizer for melt blending. In noncompatibilized blends, the dispersed phase particle size increased with SAN concentration due to coalescence effects. Static coalescence experiments showed evidence of greater coalescence in blends with higher viscosity ratios. For noncompatibilized PBT/SAN/MGE blends with high molecular weight PBT as matrix phase, the average particle size of SAN phase does not depend on the SAN concentration in the blends. However noncompatibilized blends with low molecular weight PBT showed a significant increase in SAN particle size with the SAN concentration. The effect of MGE epoxy content and MGE molecular weight on the morphology of the PBT/SAN blend was also investigated. As the MGE epoxy content increased, the average particle size of SAN initially decreased with both high and low molecular weight PBT phase, thereafter leveling off with a critical content of epoxy groups in the blend. This critical content was higher in the blends containing low molecular weight PBT than in those with high molecular weight PBT. At a fixed MGE epoxy content, a decrease in MGE molecular weight yielded PBT/SAN blends with dispersed nanoparticles with an average size of about 40 nm. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Ternary blends of phenoxy/SAN/poly(-ε-caprolactone)

The compatibilizing effect of poly(ε-caprolactone) (PCL) on the blends of two immiscible polymers, poly(hydroxy ether of bisphenol A) (phenoxy) and poly(styrene-co-acrylonitrile) (SAN) has been investigated. The phase behavior of the ternary blends was affected by the AN content in the SAN copolymers and a maximum miscible region was observed at 19.5 wt % of AN. The effect of AN content on the phase behavior of the ternary blends was interpreted in terms of the relative magnitude of the segmental interaction energy densities, which were obtained by combining a melting point depression and an extended binary interaction model. When a small amount of PCL was added to the phenoxy/SAN blends, the phase morphology showed a finer phase dispersion, indicating that the interfacial tension between the phenoxy and SAN is considerably reduced. However, the improvement in tensile properties was limited despite the morphological change with the PCL content. From the results of the DSC measurements, SEM, and tensile testing, it was understood that the PCL acted as a compatibilizer for the immiscible phenoxy/SAN blends. © 1994 John Wiley & Sons, Inc.     

Novel,well‐defined polystyrene with a fluorine cluster end‐capped group: Synthesis,characterization, and surface properties

Novel, well‐defined fluorinated polystyrene was synthesized for the first time via the controlled radical polymerization of styrene through a relatively simple process and was characterized with ¹H NMR, ¹⁹F NMR, and gel permeation chromatography. The surface properties of polystyrene and poly(acrylonitrile‐co‐butadiene‐co‐styrene) films were modified with the obtained polymers. X‐ray photoelectron spectroscopy measurements of the air‐side surface composition of the modified poly(acrylonitrile‐co‐butadiene‐co‐styrene) films showed that fluorine enriched the outermost surface, resulting in fantastic surface properties that came close to those of poly(tetrafluoroethylene). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3853–3858, 2006     

Thermal properties and toughness performance of hyperbranched‐polyimide‐modified epoxy resins

An amine‐terminated hyperbranched polyimide (HBPI) was prepared by the condensation polymerization of a commercially available triamine monomer with a dianhydride monomer. The effects of the HBPI content on the thermal and mechanical interfacial properties of diglycidyl ether of bisphenol A (DGEBA) epoxy resins were investigated with several techniques. The thermogravimetric analysis results showed that the thermal stability of the DGEBA/HBPI blends did not obviously change as the HBPI content increased. The glass‐transition temperature (T_g) of the DGEBA/HBPI blends increased with the addition of HBPI. Improvements in the critical stress intensity factor (K_IC) and impact strength of the blends were observed with the addition of HBPI. The K_IC value and impact strength were 2.5 and 2 times the values of the neat epoxy resins with only 4 wt % HBPI. The fractured surfaces were studied with scanning electron microscopy to investigate the morphology of the blends, and they showed that shear deformation occurred to prevent the propagation of cracks in the DGEBA/HBPI blends. These results indicated that a toughness improvement was achieved without a decrease in the thermal stability or T_g. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3348–3356, 2006     

Synthesis and characterization of well‐defined poly(2‐hydroxyethyl methacrylate‐co‐styrene)‐graft‐poly(ε‐caprolactone) by sequential controlled polymerization

A new graft copolymer, poly(2‐hydroxyethyl methacrylate‐co‐styrene) ‐graft‐poly(?‐caprolactone), was prepared by combination of reversible addition‐fragmentation chain transfer polymerization (RAFT) with coordination‐insertion ring‐opening polymerization (ROP). The copolymerization of styrene (St) and 2‐hydroxyethyl methacrylate (HEMA) was carried out at 60 °C in the presence of 2‐phenylprop‐2‐yl dithiobenzoate (PPDTB) using AIBN as initiator. The molecular weight of poly (2‐hydroxyethyl methacrylate‐co‐styrene) [poly(HEMA‐co‐St)] increased with the monomer conversion, and the molecular weight distribution was in the range of 1.09 ～ 1.39. The ring‐opening polymerization (ROP) of ?‐caprolactone was then initiated by the hydroxyl groups of the poly(HEMA‐co‐St) precursors in the presence of stannous octoate (Sn(Oct)₂). GPC and ¹H‐NMR data demonstrated the polymerization courses are under control, and nearly all hydroxyl groups took part in the initiation. The efficiency of grafting was very high. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5523–5529, 2004     

Effects of poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] on the charge distributions of low‐density polyethylene/polystyrene blends

The effect of the triblock copolymer poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS) on the formation of the space charge of immiscible low‐density polyethylene (LDPE)/polystyrene (PS) blends was investigated. Blends of 70/30 (wt %) LDPE/PS were prepared through melt blending in an internal mixer at a blend temperature of 220 °C. The amount of charge that accumulated in the 70% LDPE/30% PS blends decreased when the SEBS content increased up to 10 wt %. For compatibilized and uncompatibilized blends, no significant change in the degree of crystallinity of LDPE in the blends was observed, and so the effect of crystallization on the space charge distribution could be excluded. Morphological observations showed that the addition of SEBS resulted in a domain size reduction of the dispersed PS phase and better interfacial adhesion between the LDPE and PS phases. The location of SEBS at a domain interface enabled charges to migrate from one phase to the other via the domain interface and, therefore, resulted in a significant decrease in the amount of space charge for the LDPE/PS blends with SEBS. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2813–2820, 2004     

Noncovalent functionalization of multiwalled carbon nanotubes using graft copolymer with naphthalene and its application as a reinforcing filler for poly(styrene‐co‐acrylonitrile)

A new compatibilizer, poly(vinyl benzyloxy ethyl naphthalene)‐graft‐poly(methyl methacrylate), for poly(styrene‐co‐acrylonirile) (SAN)/multi‐walled carbon nanotubes (MWCNTs) composites was synthesized. It has been identified that naphthalene unit in backbone of compatibilizer interacts with MWCNTs via π? π interaction and that the PMMA graft of the compatibilizer is miscible with the SAN matrix. When a small amount of compatibilizer was added to SAN/MWCNT composites, MWCNTs were more homogeneously dispersed in SAN matrix than the case without compatibilizer, indicating that the compatibilizer improves the compatibility between SAN and MWCNTs. As a consequence, mechanical and electrical properties of the composites with compatibilizer were largely improved as compared with those of composites without compatibilizer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4184–4191, 2010     

Miscibility of polycarbonates with copolymers containing cyclohexylmethacrylate

We prepared various copolymers containing styrene and methacrylates to examine their miscibility with polycarbonates such as bisphenol A polycarbonate (PC), dimethylpolycarbonate (DMPC), and tetramethylpolycarbonate (TMPC). Among the various copolymers examined, poly(methyl methacrylate‐co‐cyclohexylmethacrylate) [P(MMA–CHMA)] copolymers containing proper amounts of cyclohexylmethacrylate (CHMA) formed miscible blends with PC and DMPC, whereas TMPC did not form a miscible blend with P(MMA–CHMA). However, TMPC was miscible with poly(styrene‐co‐cyclohexylmethacrylate) [P(S–CHMA)] copolymers containing less than about 40 wt % CHMA, whereas PC and DMPC were always immiscible with P(S–CHMA). Miscible blends exhibited lower critical solution temperature (LCST)‐type phase behavior. Binary interaction energies were calculated from the observed phase boundaries with lattice–fluid theory combined with a binary interaction model. The quantitative interaction energy of each binary pair indicated that the phenyl ring substitution of polycarbonate with methyl groups did not lead to interactions that were favorable for miscibility with methyl methacrylate (MMA) and CHMA, but it did lead to favorable interactions with styrene. The addition of CHMA to MMA initially increased the LCST but ultimately led to immiscibility with PC and DMPC; however, addition of CHMA to styrene always decreased the LCST with TMPC. The increased LCST of PC or DMPC blends stemmed from intramolecular repulsion between MMA and CHMA, whereas the decreased LCST of TMPC/P(S–CHMA) blends with CHMA content came from negative interaction energy between styrene and CHMA. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1948–1955, 2001     

Synthesis of polymeric microspheres from a Merrifield resin by surface‐initiated nitroxide‐mediated radical polymerization

Polymeric microspheres were prepared from a Merrifield resin via nitroxide‐mediated radical polymerization. Polystyrene, poly(acetoxystyrene), and poly[styrene‐b‐(methyl methacrylate‐co‐styrene)], poly(acetoxystyrene‐b‐styrene), and poly(styrene‐co‐2‐hydroxyethyl methacrylate) copolymers were demonstrated to graft onto 2,2,6,6‐tetramethyl‐1‐piperidinyloxy nitroxide bound Merrifield resins. The polymerization control was enhanced both on the surface and in solution by the addition of sacrificial nitroxide. The significant increase in the particle diameter (more than a fivefold volume increase for polystyrene brushes) showed that polymer growth was not only on the surface but also within the particles, and this diameter increase could be adjusted through changes in the molecular weight of the polymers. The microspheres were characterized by elemental analysis, IR spectroscopy, particle size analysis, and optical microscopy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2145–2154, 2005     

Microphase separation in poly(acrylonitrile–butadiene–styrene) (ABS) studied with paramagnetic spin probes. I. Electron spin resonance spectra

Microphase separation in poly(acrylonitrile–butadiene–styrene) (ABS) was studied as a function of the butadiene content and method of preparation with electron spin resonance (ESR) spectra of nitroxide spin probes. Results for the ABS polymers were evaluated by comparison with similar studies of the homopolymers polybutadiene (PB), polystyrene (PS), and polyacrylonitrile (PAN) and the copolymers poly(styrene‐co‐acrylonitrile) (SAN) and poly(styrene‐co‐butadiene) (SB). Two spin probes were selected for this study: 10‐doxylnonadecane (10DND) and 5‐doxyldecane (5DD). The probes varied in size and were selected because their hydrocarbon backbone made them compatible with the polymers studied. The ESR spectra were measured in the temperature range 120–420 K and were analyzed in terms of line shapes, line widths, and hyperfine splitting from the ¹⁴N nucleus; the appearance of more than one spectral component was taken as an indication of microphase separation. Only one spectral component was detected for 10DND in PB, PS, and PAN and in the copolymers SAN and SB. In contrast, two spectral components differing in their dynamic properties were detected for both probes in the three types of ABS samples studied and were assigned to spin probes located in butadiene‐rich domains (the fast component) and SAN‐rich domains (the slow component). The behavior of the fast component in ABS prepared by mass polymerization suggested that the low‐T_g (glass‐transition‐temperature) phase was almost pure PB. The corresponding phase in ABS prepared by emulsion grafting also contained styrene and acrylonitrile monomers. A redistribution of the spin probes on heating occurred with heating near the T_g of the SAN phase, suggesting that the ABS polymers as prepared were not in thermodynamic equilibrium. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 415–423, 2002; DOI 10.1002/polb.10109     

Crystallization in PHB/DGEBA blends

Real‐time experiments using small‐angle X‐ray scattering and differential scanning calorimetry on blends of the semicrystalline polyester poly(3‐hydroxybutyrate) (PHB) and amorphous monomer epoxy DGEBA (diglycidyl ether of bisphenol A) were performed. Differences in the processes of melting and re‐crystallization were observed in blends relative to pure PHB. The results obtained in this study indicated that re‐crystallization is more important in blends with 50% DGEBA than in pure PHB. Moreover, segregation toward the interfibrillar region would facilitate re‐crystallization. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 882–886     

One‐stage synthesis of narrowly dispersed polymeric core‐shell microspheres

A method of one‐stage soap‐free emulsion polymerization to synthesize narrowly dispersed core‐shell microspheres is proposed. Following this method, core‐shell microspheres of poly(styrene‐co‐4‐vinylpyridine), poly(styrene‐co‐methyl acrylic acid), and poly[styrene‐co‐2‐(acetoacetoxy)ethyl methacrylate‐co‐methyl acrylic acid] are synthesized by one‐stage soap‐free emulsion polymerization of a mixture of one or two hydrophobic monomers and a suitable hydrophilic monomer in water. The effect of the molar ratio of the hydrophobic monomer to the hydrophilic one on the size, the core thickness, and the shell thickness of the core‐shell microspheres is discussed. The molar ratio of the hydrophobic and hydrophilic monomers and the hydrophilicity of the resultant oligomers of the hydrophilic monomer are optimized to synthesize narrowly dispersed core‐shell microspheres. A possible mechanism of one‐stage soap‐free emulsion polymerization to synthesize core‐shell microspheres is suggested and coagglutination of the oligomers of the hydrophilic monomers on the hydrophobic core is considered to be the key to form core‐shell microspheres. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1192–1202, 2008     

Complex phase behavior and state of miscibility in Poly(ethylene glycol)/Poly(l‐lactide‐co‐ε‐caprolactone) Blends

A miscibility and phase behavior study was conducted on poly(ethylene glycol) (PEG)/poly(l ‐lactide‐ε‐caprolactone) (PLA‐co‐CL) blends. A single glass transition evolution was determined by differential scanning calorimetry initially suggesting a miscible system; however, the unusual T_g bias and subsequent morphological study conducted by polarized light optical microscopy (PLOM) and atomic force microscopy (AFM) evidenced a phase separated system for the whole range of blend compositions. PEG spherulites were found in all blends except for the PEG/PLA‐co‐CL 20/80 composition, with no interference of the comonomer in the melting point of PEG (T_m = 64 °C) and only a small one in crystallinity fraction (X_c = 80% vs. 70%). However, a clear continuous decrease in PEG spherulites growth rate (G) with increasing PLA‐co‐CL content was determined in the blends isothermally crystallized at 37 °C, G being 37 µm/min for the neat PEG and 12 µm/min for the 20 wt % PLA‐co‐CL blend. The kinetics interference in crystal growth rate of PEG suggests a diluting effect of the PLA‐co‐CL in the blends; further, PLOM and AFM provided unequivocal evidence of the interfering effect of PLA‐co‐CL on PEG crystal morphology, demonstrating imperfect crystallization in blends with interfibrillar location of the diluting amorphous component. Significantly, AFM images provided also evidence of amorphous phase separation between PEG and PLA‐co‐CL. A true T_g vs. composition diagram is proposed on the basis of the AFM analysis for phase separated PEG/PLA‐co‐CL blends revealing the existence of a second PLA‐co‐CL rich phase. According to the partial miscibility established by AFM analysis, PEG and PLA‐co‐CL rich phases, depending on blend composition, contain respectively an amount of the minority component leading to a system presenting, for every composition, two T_g's that are different of those of pure components. © 2013 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys. 2014 , 52, 111–121